CN108534463A - Polycrystalline silicon reduction exhaust deep-purifying method and system - Google Patents

Polycrystalline silicon reduction exhaust deep-purifying method and system Download PDF

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CN108534463A
CN108534463A CN201710123404.3A CN201710123404A CN108534463A CN 108534463 A CN108534463 A CN 108534463A CN 201710123404 A CN201710123404 A CN 201710123404A CN 108534463 A CN108534463 A CN 108534463A
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gas
hydrogen chloride
chlorosilane
liquid
tower
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CN108534463B (en
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蒋鹏
陈国辉
陈喜清
杜新
王玉丽
颉刚刚
刘想林
马金杉
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Xinte Energy Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1406—Multiple stage absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1431—Pretreatment by other processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/10—Hydrogen

Abstract

The present invention provides a kind of polycrystalline silicon reduction exhaust deep-purifying method, including：Reduction tail gas is set to pass through multistage cooling treatment successively, to export gas-liquid mixture；Gas-liquid separation processing is carried out to the gas-liquid mixture, and cooling treatment is carried out to reduction tail gas using the cold for the gaseous mixture isolated；In two-stage hydrogen chloride absorption tower absorption processing is carried out using the hydrogen chloride in the gaseous mixture that top-down chlorosilane lean solution has been utilized cold in tower；Dissection process is carried out to the chlorosilane rich solution of hydrogen chloride absorption tower tower reactor output in hydrogen chloride Analytic Tower, and light component is exported from tower reactor output chlorosilane lean solution, tower top；Cooling treatment is carried out to the chlorosilane lean solution that hydrogen chloride Analytic Tower tower reactor exports using the cold of the chlorosilane rich solution of two-stage hydrogen chloride absorption tower tower reactor output.Correspondingly, a kind of advanced purification system is provided.While the present invention makes the quality of recycling hydrogen meet the corresponding requirements of electronic-grade polycrystalline silicon, the load that additional cold consumes, mitigates absorption tower is reduced.

Description

Polycrystalline silicon reduction exhaust deep-purifying method and system
Technical field
The present invention relates to technical field of polysilicon production, and in particular to a kind of polycrystalline silicon reduction exhaust deep-purifying method and A kind of polycrystalline silicon reduction exhaust advanced purification system.
Background technology
In the epoch of the worsening shortages of fossil energy instantly, the emergence of novel energy has become inexorable trend.Polysilicon conduct The key raw material of integrated circuit and photovoltaic generation is the basic material of national new energy development.However, as novel energy The production of basic material, polysilicon is a kind of production process of high energy consumption, moreover, also more next to the standard of polysilicon quality requirement It is higher.With the formulation of polysilicon grading standard, the challenge of bigger is proposed to the quality requirement of polysilicon.
Currently, polysilicon mainly uses improved Siemens (i.e. trichlorosilane reduction method) to produce, refer to utilizing gas phase Sedimentation passes through H in reduction furnace2To restore SiHCl3To prepare polysilicon, specific reaction equation is：
3SiHCl3+H2→2Si+5HCl+SiCl4
Since the conditions such as temperature in reduction furnace are extremely difficult to uniform, cause actual reduction process sufficiently complex, and companion Occur with side reaction, the ingredient for allowing for reduction tail gas in this way is complex, including hydrogen, hydrogen chloride gas, gas phase chlorosilane With a small amount of impurity etc., wherein gas phase chlorosilane is SiHCl3(also referred to as TCS), SiCl4(also referred to as STC) and SiH2Cl2(also referred to as For DCS) gaseous mixture.
Currently, domestic many enterprises all suffer from, polysilicon product is of low quality, and the predicament of unstable product quality makes Must be promoted and stablize polysilicon product quality is particularly important.By analyzing the factor for influencing polysilicon product quality It is found that quality of one of key factor from main material trichlorosilane, another key factor is come since reduction tail The quality of the hydrogen recycled in gas.
Wherein, the recycling of tail gas is restored mainly using improvement Siemens Dry recovery technique.Specifically process includes：Also protocercal tail Gas liquefies gas phase chlorosilane to be detached with hydrogen, hydrogen chloride gas after low pressure condenses, the hydrogen isolated and chlorination The gaseous mixture of hydrogen is sent after compressor carries out compression boosting to using liquid-phase chlorosilane as in the absorption tower of absorbing liquid, will be described Absorbing hydrogen chloride gas in gaseous mixture, and the chlorosilane rich solution containing hydrogen chloride is exported from tower reactor, it is then fed into analytical process Dissection process is carried out, liquid-phase chlorosilane and hydrogen chloride gas are detached, and unabsorbed hydrogen and few in the gaseous mixture It measures impurity to export from tower top, is then sent to activated carbon and molecular sieve adsorption column carries out adsorption treatment, it is miscellaneous in hydrogen by being blended in Pure hydrogen is removed divided by obtained to matter, should be activated after adsorption column use with reuse, above step move in circles to The Dry recovery system continuously recycled is formed, and Dry recovery system becomes the important of guarantee polysilicon purity to the purification of hydrogen Part.
However, it is found by the inventors that：
Influence factor in conjunction with the hydrogen quality of the consumption degree and recycling of cold is analyzed it is found that being condensed in low pressure Generally use freon carries out deep condensation to reduction tail gas in the process, needs to consume a large amount of cold, and be directly entered suction The hydrogen chloride gas received in the gaseous mixture in tower is more, to increase the load on absorption tower；
Moreover, because needing the environment of cryogenic high pressure could be a large amount of by the hydrogen chloride gas in the gaseous mixture in absorption tower Removal, but northern season temperature change is larger so that the temperature in absorption tower is unstable, the hydrogen quality for causing tower top to export Fluctuation it is larger, further result in adsorption column delay time increase；
In addition, carbon molecules can be carried secretly in the purified hydrogen that the hydrogen of tower top output obtains after activated carbon adsorption, use The concentration of carbon of polysilicon can be influenced when the hydrogen gas production polysilicon of this entrainment carbon molecules so that the quality of polysilicon is unable to get It is effectively promoted, the polysilicon of production is caused to cannot be satisfied corresponding requirements (hydrogen chloride content ＜ 50ppm, the carbon of electronic-grade polycrystalline silicon Content ＜ 3ppm).
Invention content
The technical problem to be solved by the present invention is to for the drawbacks described above in the presence of the prior art, providing one kind makes back While the quality of receipts hydrogen meets the corresponding requirements of electronic-grade polycrystalline silicon, additional cold consumption can be reduced, mitigate absorption The polycrystalline silicon reduction exhaust deep-purifying method and system of the load of tower, the delay time of reduction adsorption column.
Technical solution is used by solving present invention problem：
The present invention provides a kind of polycrystalline silicon reduction exhaust deep-purifying method, the reduction tail gas include hydrogen, hydrogen chloride, The gaseous mixture of chlorosilane and a small amount of impurity comprising following steps：
Make multistage cooling treatment of the reduction tail gas successively by multistage cooling equipment, to be formed and export gas-liquid mixed Object comprising hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of impurity gaseous mixture and condensed liquid phase Chlorosilane；
Gas-liquid separation processing is carried out to the gas-liquid mixture of multistage cooling equipment output using the first lime set storage tank, it should The gaseous mixture of hydrogen, hydrogen chloride, the gas phase chlorosilane and a small amount of impurity that are not condensed in gas-liquid mixture and condensed liquid Phase chlorosilane detaches, and then send the condensed liquid-phase chlorosilane to downstream rectification working process, and in the cooling equipment of multistage Cooling treatment is carried out to the reduction tail gas using the cold of the gaseous mixture from the first lime set storage tank；
Using top-down chlorosilane lean solution in tower to from the first lime set storage tank in two-stage hydrogen chloride absorption tower And cold carries out absorption processing by the hydrogen chloride in the gaseous mixture of multistage cooling equipment utilization, and it is rich from tower reactor output chlorosilane Liquid exports fixed gas from tower top, then the adsorption treatment for making the fixed gas pass through active carbon adsorption column and silica gel adsorption column successively To form pure hydrogen, then the pure hydrogen is sent to upstream production of polysilicon process；
Dissection process is carried out to the chlorosilane rich solution of two-stage hydrogen chloride absorption tower tower reactor output in hydrogen chloride Analytic Tower, and Chlorosilane lean solution is exported from tower reactor, light component is exported from tower top, then send the light component to downstream rectification working process；
Using the cold of the chlorosilane rich solution of two-stage hydrogen chloride absorption tower tower reactor output to hydrogen chloride in liquid-liquid heat exchanger The chlorosilane lean solution of Analytic Tower tower reactor output carries out cooling treatment, and chlorosilane lean solution after cooling is then sent into two-stage hydrogen chloride and is inhaled Tower top is received, and the cold from two-stage hydrogen chloride absorption tower tower reactor has been sent by the chlorosilane rich solution that liquid-liquid heat exchanger utilizes Enter hydrogen chloride Analytic Tower.
The present invention also provides a kind of polycrystalline silicon reduction exhaust advanced purification system, the reduction tail gas includes hydrogen, chlorination The gaseous mixture of hydrogen, chlorosilane and a small amount of impurity, the purification system include：The cooling equipment of multistage, the first lime set storage tank, two-stage chlorine Change hydrogen absorption tower, active carbon adsorption column, silica gel adsorption column, hydrogen chloride Analytic Tower and liquid-liquid heat exchanger,
The multistage cooling equipment is used to pass through the reduction tail gas successively the multistage cooling treatment of multistage cooling equipment, To be formed and export gas-liquid mixture comprising the mixing of hydrogen, hydrogen chloride, the gas phase chlorosilane and a small amount of impurity that are not condensed Gas and condensed liquid-phase chlorosilane；
The first lime set storage tank is used to carry out gas-liquid separation processing to the gas-liquid mixture of multistage cooling equipment output, with By in the gas-liquid mixture hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of impurity gaseous mixture with it is condensed Liquid-phase chlorosilane separation, the condensed liquid-phase chlorosilane is sent to downstream rectification working process, the multistage cooling equipment profit Cooling treatment is carried out to the reduction tail gas with the cold of the gaseous mixture from the first lime set storage tank；
The two-stage hydrogen chloride absorption tower is used to store up to coming from the first lime set using top-down chlorosilane lean solution in tower Tank and cold absorption processing is carried out by the hydrogen chloride in the gaseous mixture of multistage cooling equipment utilization, and export chlorine silicon from tower reactor Alkane rich solution exports fixed gas from tower top；
The active carbon adsorption column and the silica gel adsorption column are orderly used to carries out adsorption treatment and shape to the fixed gas At pure hydrogen, the pure hydrogen is sent to upstream production of polysilicon process；
The chlorosilane rich solution that the hydrogen chloride Analytic Tower is used to export the two-stage hydrogen chloride absorption tower tower reactor solves Analysis is handled, and exports chlorosilane lean solution from tower reactor, exports light component from tower top, the light component is sent to downstream rectification working process；
The liquid-liquid heat exchanger is used for the cold of the chlorosilane rich solution using two-stage hydrogen chloride absorption tower tower reactor output Cooling treatment is carried out to the chlorosilane lean solution of hydrogen chloride Analytic Tower tower reactor output, is then sent into chlorosilane lean solution after cooling The two-stage hydrogen chloride absorption tower top, and by the cold from the two-stage hydrogen chloride absorption tower tower reactor by the liquid liquid The chlorosilane rich solution that heat exchanger utilizes is sent into the hydrogen chloride Analytic Tower.
Advantageous effect：
Polycrystalline silicon reduction exhaust deep-purifying method of the present invention and system produce more for existing improved Siemens Deficiency is improved present in the reduction exhaust gas recovery system used when crystal silicon, can to reduction tail gas carry out deep purifying, Removal of impurities reduces the impurity content in recycling hydrogen, promotes the quality of recycling hydrogen, to meet electricity in the quality for making recycling hydrogen While the corresponding requirements of sub- level polysilicon, additionally it is possible to reduce additional cold consumption, the load on mitigation absorption tower, reduction absorption The delay time of column reduces the cost and energy consumption of production of polysilicon.
Description of the drawings
Fig. 1 is the flow chart for the polycrystalline silicon reduction exhaust deep-purifying method that the embodiment of the present invention 1 provides；
Fig. 2 is the flow chart for the polycrystalline silicon reduction exhaust deep-purifying method that the embodiment of the present invention 2 provides；
Fig. 3 is a kind of schematic diagram for polycrystalline silicon reduction exhaust advanced purification system that the embodiment of the present invention 3 provides；
Fig. 4 is the schematic diagram for another polycrystalline silicon reduction exhaust advanced purification system that the embodiment of the present invention 3 provides；
Fig. 5 is a kind of schematic diagram for polycrystalline silicon reduction exhaust advanced purification system that the embodiment of the present invention 4 provides；
Fig. 6 is the schematic diagram for another polycrystalline silicon reduction exhaust advanced purification system that the embodiment of the present invention 4 provides.
In figure：1- restores tail gas；The first water coolers of 2-；3- gas-gas heat exchangers；4- the first lime set storage tanks；5- first Delivery pump；6- brine condensers；The first freon condensers of 7-；8- the second lime set storage tanks；The second delivery pumps of 9-；10- is pressed Contracting machine；11- the first hydrogen chloride absorption towers；12- the second hydrogen chloride absorption towers；13- liquid-liquid heat exchangers；14- hydrogen chloride parses Tower；The second water coolers of 15-；16- circulating pumps；The second freon condensers of 17-；18- deep freezers；19- activated carbon adsorptions Column；20- silica gel adsorption columns；a、b、c、d、e、f、g、h、i、j、k、k1、k2、m、n、o1、o2、p1、p2、q、r、s、t、u、v、w、 X, x1, x2, y, z, z1, z2- pipeline.
Specific implementation mode
To make those skilled in the art more fully understand technical scheme of the present invention, with reference to the accompanying drawings and examples to this Invention is described in further detail.
Currently, improvement Siemens Dry recovery technology is mostly used greatly when reduction tail gas recycle treatment process recycling hydrogen, with This removes the impurity in recycling hydrogen, but is reach the corresponding requirements of electronic-grade polycrystalline silicon as possible in the actual production process, It is very strict to the operating parameter requirement on absorption tower, while making using increase absorbing liquid internal circulating load, reduction absorbing liquid temperature and only The mode of the hydrogen chloride and impurity in recycling hydrogen is removed with active carbon adsorption column, such mode is for energy saving and recycling hydrogen Purification is not optimal effect.
Based on the above issues, the deep-purifying method and system of polycrystalline silicon reduction exhaust are inventors herein proposed, and in particular to Application in electronic-grade polycrystalline silicon production about the research and the technological process of the purification technique of recycling hydrogen in production, this hair It is bright compared with existing general improvement Siemens solvent recovery technology from vent gas, by by the chlorosilane just detached remove, increase two-stage It absorbs, and increases silica gel adsorption column, effectively saved the consumption of low-pressure area cold, while the impurity in hydrogen will be recycled It is efficiently separated and is removed, improved the quality of recycling hydrogen, also save a large amount of cold, solve production of polysilicon Highly energy-consuming and the recycling inferior problem of hydrogen, improve polysilicon product matter when restoring tail gas clean-up separation, impurity removal in system Amount, reduces the production cost of enterprise, enterprise core competitiveness.It is described in detail below by specific embodiment.
It should be noted that the rectification working process and production of polysilicon process that are referred in the present invention are existing process, thus It repeats no more.
Embodiment 1：
The present embodiment provides a kind of polycrystalline silicon reduction exhaust deep-purifying method, the reduction tail gas comes from upstream polysilicon Production process specifically includes the gaseous mixture of hydrogen, hydrogen chloride, chlorosilane and a small amount of impurity, wherein chlorosilane includes four chlorinations The gaseous mixture of silicon, trichlorosilane and dichlorosilane, the impurity include phosphorus, boron, iron etc., and impurity containing in restoring tail gas Amount is 2ppm~5ppm.
As shown in Figure 1, the purification method includes the following steps S101 to step S105.
S101. make multistage of the reduction tail gas from upstream production of polysilicon process successively by multistage cooling equipment Cooling treatment, to be formed and export gas-liquid mixture comprising hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of The gaseous mixture of impurity and condensed liquid-phase chlorosilane.
In this step, the multistage cooling equipment includes that at least two-stage cools down equipment.
S102. gas-liquid separation processing is carried out to the gas-liquid mixture of multistage cooling equipment output using the first lime set storage tank, With by the gas-liquid mixture hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of impurity gaseous mixture with it is cold Solidifying liquid-phase chlorosilane separation, then send the condensed liquid-phase chlorosilane to downstream rectification working process, with to liquid phase chlorine silicon Trichlorosilane, silicon tetrachloride in alkane and dichlorosilane carry out separating-purifying, and using from the in the cooling equipment of multistage The cold of the gaseous mixture of one lime set storage tank carries out cooling treatment to the reduction tail gas.
S103. it is stored up using top-down chlorosilane lean solution in tower to coming from the first lime set in two-stage hydrogen chloride absorption tower Tank and cold absorption processing is carried out by the hydrogen chloride in the gaseous mixture of multistage cooling equipment utilization, and export chlorine silicon from tower reactor Alkane rich solution exports fixed gas from tower top, then the absorption for making the fixed gas pass through active carbon adsorption column and silica gel adsorption column successively Then processing is sent the pure hydrogen to upstream production of polysilicon process with forming pure hydrogen.
In this step, the fixed gas exported from two-stage hydrogen chloride absorption column overhead is the hydrogen containing a small amount of impurity, warp After crossing the adsorption treatment of active carbon adsorption column, impurity therein can be effectively removed, but can also introduce carbon impurity simultaneously, using After the adsorption treatment of silica gel adsorption column, carbon impurity can be effectively removed, to obtain pure hydrogen.Then pure by what is obtained Hydrogen be sent into upstream production of polysilicon process, to prepare polysilicon.
In addition, the connection type of the two-stage hydrogen chloride absorption tower is specially：To be input to two-stage hydrogen chloride absorption tower Gaseous mixture when meeting preset condition, the two-stage hydrogen chloride absorption tower is connected in parallel；To be input to two-stage hydrogen chloride absorption When the gaseous mixture of tower does not meet preset condition, the two-stage hydrogen chloride absorption tower is connected in series with.Certainly, two-stage hydrogen chloride absorption tower Be connected in parallel and be connected in series with and can switch at any time, you can at any time will be in parallel two-stage hydrogen chloride absorption tower switch To be connected in series with mode, also can the two-stage hydrogen chloride absorption tower in the mode that is connected in series be switched to the side of being connected in parallel at any time Formula can specifically be realized by pipeline and the control of simple valve.
More preferably, the preset condition is：Into the content of hydrogen chloride gas in the gaseous mixture of two-stage hydrogen chloride absorption tower Within 50ppm, the total content of phosphorus, boron and iron tramp is within 1ppm.
In practical applications, also connection type in parallel or series can be selected according to actual production demand, to improve reality Flexibility in the production of border and production of units efficiency, the continuous and stable operation of safeguards system high efficiency, high quality.For example, being When system is contaminated or there is fluctuation, may be selected to be connected in series in start-up, the quality of the recycling hydrogen of tower top output at this time Mode improves hydrogen quality to increase absorption tower height degree；The side of being connected in parallel may be selected when the hydrogen quality of tower top output is stablized Formula improves absorption tower treating capacity to increase absorption tower tower diameter.The quality of hydrogen is usually to stablize under certain normal operation , parallel running mode is preferentially selected at this time, to improve production capacity.
Wherein, the parallel of the two-stage hydrogen chloride absorption tower refers to cold by the cooling equipment profit of multistage Gaseous mixture is input to two hydrogen chloride absorption towers, and the fixed gas mixing of this two hydrogen chloride absorption column overhead outputs simultaneously Pass through the adsorption treatment of active carbon adsorption column and silica gel adsorption column, the chlorine of this two hydrogen chloride absorption tower tower reactors output successively again afterwards It is re-fed into liquid-liquid heat exchanger after the mixing of silane rich solution；The mode that is connected in series with of the two-stage hydrogen chloride absorption tower refers to cold The gaseous mixture by multistage cooling equipment utilization is merely entered to the second hydrogen chloride absorption tower, defeated from the second hydrogen chloride absorption column overhead The fixed gas gone out is input to the first hydrogen chloride absorption tower again, and the fixed gas exported from the first hydrogen chloride absorption column overhead passes through successively The adsorption treatment of active carbon adsorption column and silica gel adsorption column, and the tower reactor of the first hydrogen chloride absorption tower and the second hydrogen chloride absorption tower It is re-fed into liquid-liquid heat exchanger after the chlorosilane rich solution mixing of output.
S104. the chlorosilane rich solution of two-stage hydrogen chloride absorption tower tower reactor output is carried out at parsing in hydrogen chloride Analytic Tower Reason, and chlorosilane lean solution is exported from tower reactor, light component is exported from tower top, then send the light component to downstream rectification working process.
In the present embodiment, the light component exported from hydrogen chloride Analytic Tower includes mainly hydrogen chloride gas, is also possible to wrap certainly Micro impurity is included, such as micro dichlorosilane, after rectification working process carries out purification processes to it, can remove therein miscellaneous Matter obtains the higher hydrogen chloride gas of purity.
S105. the cold of the chlorosilane rich solution exported using two-stage hydrogen chloride absorption tower tower reactor in liquid-liquid heat exchanger is to chlorine The chlorosilane lean solution for changing the output of hydrogen Analytic Tower tower reactor carries out cooling treatment, and chlorosilane lean solution after cooling is then sent into two-stage chlorination Hydrogen absorption tower top, and the chlorosilane that the cold from two-stage hydrogen chloride absorption tower tower reactor has been utilized by liquid-liquid heat exchanger are rich Liquid is sent into hydrogen chloride Analytic Tower.
It should be noted that the step of step S101 to S105 in the present embodiment sequence does not absolutely represent each step and exists Sequencing when execution.
Polycrystalline silicon reduction exhaust deep-purifying method described in the present embodiment is effectively utilized what the first lime set storage tank was isolated The cold of the chlorosilane rich solution of cold and two-stage hydrogen chloride absorption tower the tower reactor output of gaseous mixture, both has preferable separating effect (isolating liquid-phase chlorosilane, hydrogen and hydrogen chloride successively), and system cold is fully utilized, therefore public work cold consumes It is few, to reduce production cost；Using silica gel adsorption column by active carbon adsorption column treated the hydrogen containing carbon impurity again Secondary carry out adsorption treatment, has effectively removed carbon impurity therein so that recycling hydrogen is meeting accordingly wanting for electronic-grade polycrystalline silicon While asking (hydrogen chloride content ＜ 50ppm, carbon content ＜ 3ppm), the impurity content entrained by recycling hydrogen is effectively reduced, And reduce active carbon adsorption column delay time, active carbon adsorption column usage time is increased, recycling hydrogen purification is reduced Time.
Embodiment 2：
The present embodiment provides a kind of polycrystalline silicon reduction exhaust deep-purifying methods.As shown in Fig. 2, the purification method includes Following steps S201 to step S213.
It should be noted that the first water cooler, gas-gas heat exchanger, the first lime set storage tank involved in following step, first Delivery pump, brine condenser, the first freon condenser, the second lime set storage tank and the second delivery pump are all located at low-pressure area, pressure Ranging from 0.3~0.5MPa, preferably 0.45MPa.And compressor, two-stage hydrogen chloride absorption tower, liquid-liquid heat exchanger, chlorination hydrogenolysis Analysis tower, the second water cooler, circulating pump, the second freon condenser, deep freezer, active carbon adsorption column and silica gel adsorption column are all located at Higher-pressure region, the pressure limit that wherein two-stage hydrogen chloride absorption tower uses is 1.4~1.7MPa, preferably 1.6MPa；Chlorination hydrogenolysis The pressure limit that analysis tower uses is 0.7~0.9MPa, preferably 0.8MPa；The operating temperature range of active carbon adsorption column is -20 ~-50 DEG C, preferably -35 DEG C.
S201. cooling place is carried out to the reduction tail gas from upstream production of polysilicon process using the first water cooler Reason, to be formed and export gas-liquid mixture.
It should be noted that in the present invention " gas-liquid mixture " of nearly all appearance all include hydrogen, hydrogen chloride, not by The gas phase chlorosilane of condensation and the gaseous mixture of a small amount of impurity and condensed liquid-phase chlorosilane, only different gas-liquid mixtures The accounting of middle each component is different.Wherein, the cooling medium of the first water cooler is recirculated water；The gas-liquid mixed of first water cooler output 95% is gas phase in object.
In this step, the temperature range of the reduction tail gas is 180~200 DEG C, and the reduction tail gas under the temperature range is The reduction tail gas of reduction furnace output obtain after preliminary cooling treatment, otherwise, it is excessively high to restore heater outlet temperature, is unfavorable for Later stage recycles.
Tail gas is restored after the cooling treatment of the first water cooler, temperature is greatly reduced, specially 40~50 DEG C, just In the recycling of follow-up cold.
In addition, in order to ensure that the temperature of the gas-liquid mixture of the first water cooler output meets above-mentioned temperature range requirements, compared with Excellently, the temperature for measuring and showing gas-liquid mixture in the export pipeline of the first water cooler in real time using temperature display meter, when When its temperature measured exceeds above-mentioned temperature range, it can increase and be input to the cold of the first water cooler with to the gas-liquid in it The temperature of mixture is adjusted, to meet the requirement of above-mentioned temperature range.
S202. the first water of cold pair from the second lime set storage tank (gaseous mixture isolated) is utilized in gas-gas heat exchanger The gas-liquid mixture (i.e. the first water cooler reduction tail gas after cooling) of cooler output carries out cooling treatment, and exports gas-liquid mixed Object.
Wherein, 70% is gas phase in the gas-liquid mixture that gas-gas heat exchanger exports；The gas-liquid mixed of gas-gas heat exchanger output The temperature range of object is -10~-15 DEG C.
After abovementioned steps S201 and S202, that is, restore tail gas successively pass through the first water cooler, gas-gas heat exchanger it is cold But after handling, the gas-liquid mixture of formation flows into the first lime set storage tank by way of gravity flow.
S203. utilize the gas-liquid mixture that the first lime set storage tank exports gas-gas heat exchanger (i.e. after gas-gas heat exchanger cooling Reduction tail gas) carry out gas-liquid separation processing, by the hydrogen in the gas-liquid mixture, hydrogen chloride, the gas phase chlorine not being condensed The gaseous mixture of silane and a small amount of impurity is detached with condensed liquid-phase chlorosilane, then send the condensed liquid-phase chlorosilane To downstream rectification working process, to carry out separating-purifying to trichlorosilane, silicon tetrachloride and the dichlorosilane in liquid-phase chlorosilane.
To meet the operating pressure (0.7MPaG or so) of downstream rectification working process, in the present embodiment, with the first lime set storage tank Tank bottom connection pipeline on be additionally provided with the first delivery pump, the liquid pressure range of output is 1.0~1.5MPaG, through first Liquid-phase chlorosilane after delivery pump pressurization is sent again to downstream rectification working process.
By abovementioned steps S201~S203, reduction tail gas is after level-one water cooler and gas-gas heat exchanger, wherein one Point chlorosilane is condensed, and also effectively reduces dissolved hydrogen therein, then by the first lime set storage tank carry out gas-liquid separation it Afterwards, condensed liquid-phase chlorosilane is separated, no longer carries out subsequent subzero treatment, and be fed directly to downstream rectification working process Progress separating treatment, and gaseous mixture (i.e. hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of impurity not being condensed Gaseous mixture) as by preliminary condensed gas be sent into brine condenser.
S204. cooling treatment is carried out using the gaseous mixture that brine condenser pair the first lime set storage tank is isolated, to be formed simultaneously Export gas-liquid mixture.
Wherein, the cooling medium of brine condenser is chilled brine.
In this step, 95% or so is gas phase in the gas-liquid mixture of brine condenser output, to store up the first lime set Most of chlorosilane condensate in the gaseous mixture that tank is isolated gets off.And.The temperature of the gas-liquid mixture of brine condenser output Ranging from -20~-23 DEG C of degree.
S205. cooling treatment is carried out to the gas-liquid mixture that brine condenser exports using the first freon condenser, with Gas-liquid mixture is formed and exported, and is sent into the second lime set storage tank.
In this step, other gas-liquids occurred in the gas-liquid mixture and the present embodiment of the output of the first freon condenser are mixed The ingredient for closing object is slightly different comprising hydrogen, the gaseous mixture of hydrogen chloride and a small amount of impurity and condensed liquid phase chlorine silicon Alkane, wherein be also 95% or so being gas phase, and ranging from -35~-40 DEG C of gas-liquid mixture degree.
(can be described as chlorosilane pre-separation) is detached since a chlorosilane being completed in step S203, and will be separated Liquid-phase chlorosilane send correspondingly reduced to downstream rectification working process chilled brine in step S204 cold consumption and step The cold consumption of freon in S205 saves compared with the technique that existing general reduction tail gas dry process recovery system uses About 20% cold.
S206. cooling treatment is carried out using the gas-liquid mixture of second the first freon condenser of lime set storage tank pair output, The gaseous mixture of hydrogen, hydrogen chloride and a small amount of impurity in the gas-liquid mixture to be detached with condensed liquid-phase chlorosilane.
By the cooling treatment of brine condenser in step S204, and by the first freon condenser in step S205 Further cooling treatment after, in gaseous mixture that the first lime set storage tank is isolated (i.e. aforementioned by preliminary condensed gas) Chlorosilane almost all condense out, to efficiently separate out by the light component in preliminary condensed gas, that is, realize The gaseous mixture of only hydrogen, the hydrogen chloride and a small amount of impurity for being completely separated, and not coagulating of light component and chlorosilane, using step The separating treatment of second lime set storage tank in S206 in time opens the mixed gas separation of not solidifying hydrogen, hydrogen chloride and a small amount of impurity Come.
S207. the gaseous mixture that the second lime set storage tank is isolated and cold has been utilized by gas-gas heat exchanger is sent into two-stage chlorine Change hydrogen absorption tower, and the liquid-phase chlorosilane that the second lime set storage tank is isolated is sent into higher-pressure region.
In this step, the temperature model of gaseous mixture that the second lime set storage tank is isolated and that cold has been utilized by gas-gas heat exchanger Enclose is 5~10 DEG C.
In the present embodiment, the liquid-phase chlorosilane that the first lime set storage tank is isolated is fed into the rectification working process in downstream, and not as The liquid-phase chlorosilane that second lime set storage tank is isolated out like that is sent into hydrogen chloride Analytic Tower, is to mitigate hydrogen chloride Analytic Tower Load.
In order to preferably meet the operating pressure of two-stage hydrogen chloride absorption tower, more preferably, the second lime set storage tank is made to isolate And cold be re-fed into the two-stage chlorine of higher-pressure region after the boosting of compressor processing by gaseous mixture that gas-gas heat exchanger utilizes Change hydrogen absorption tower.In the present embodiment, the pressure limit of the gaseous mixture of compressor output is 1.5-1.7MPaG.
In addition, in order to preferably meet the operating pressure of hydrogen chloride Analytic Tower, more preferably, the second lime set storage tank is made to isolate Liquid-phase chlorosilane by the second delivery pump boosting processing after sent again to higher-pressure region.The pressure of the liquid of second delivery pump output Ranging from 1.8~2.0MPaG.
S208. top-down the second lime set of chlorosilane lean solution pair storage tank point in tower is utilized in two-stage hydrogen chloride absorption tower Separate out and cold by gas-gas heat exchanger using gaseous mixture eluted, to absorb hydrogen chloride therein, from tower reactor export Chlorosilane rich solution is exported from tower top output fixed gas (hydrogen containing a small amount of impurity), and by two-stage hydrogen chloride absorption tower tower reactor Chlorosilane rich solution mixed with the liquid-phase chlorosilane that the second lime set storage tank is isolated after formed chlorosilane mixed liquor.
It has been described in detail in embodiment 1 as the specific connection type of two-stage hydrogen chloride absorption tower, details are not described herein again. When two-stage hydrogen chloride absorption tower uses parallel, the amount for being input to the gaseous mixture on every absorption tower can be according to equipment reality Border situation (such as quality, the produce load of the recycling hydrogen of tower top output) is adjusted, can be simultaneously when system throughput is big Increase the air inflow of two-stage hydrogen chloride absorption tower.
In this step, gaseous mixture and (from the top entrance of hydrogen chloride absorption tower) tower into two-stage hydrogen chloride absorption tower are interior certainly Chlorosilane lean solution under above is in contact so that hydrogen chloride is dissolved in liquid-phase chlorosilane, to effectively remove the mixing Hydrogen chloride gas in gas improves the purity of hydrogen.
S209. the fixed gas that the tower top of two-stage hydrogen chloride absorption tower exports is made to pass through active carbon adsorption column and silica gel suction successively Then the adsorption treatment of attached column is sent the pure hydrogen to upstream production of polysilicon process with forming pure hydrogen.It is living Property charcoal adsorption column and silica gel adsorption column be used in series, and the adsorbent of active carbon adsorption column be activated carbon, the suction of silica gel adsorption column Attached dose is silica gel.
In this step, the fixed gas exported from two-stage hydrogen chloride absorption column overhead is to contain a small amount of impurity (such as phosphorus, boron, iron With micro chlorosilane etc.) hydrogen, after the adsorption treatment of active carbon adsorption column, can effectively remove phosphorus therein, Impurity such as boron, iron and micro chlorosilane, but can also introduce carbon impurity simultaneously, using with the concatenated silica gel of active carbon adsorption column The adsorption treatment of adsorption column can effectively remove carbon impurity, and recycling hydrogen is made to obtain the adsorption cleaning of depth, pure to obtain , the recycling hydrogen for reaching qualified index, wherein content ＜ 50ppm, carbon content the ＜ 3ppm of hydrogen chloride.Then pure by what is obtained Net recycling hydrogen is sent into the production of polysilicon process of upstream, to prepare polysilicon.
In addition, in order to preferably meet the operating temperature of active carbon adsorption column and silica gel adsorption column, the suction of adsorption column is improved Attached effect, more preferably, make the fixed gas that two-stage hydrogen chloride absorption column overhead exports after the cooling of deep freezer processing again successively Pass through active carbon adsorption column and silica gel adsorption column so that active carbon adsorption column remove at low ambient temperatures recycling hydrogen in phosphorus, The impurity such as boron, iron, and these impurity are assembled at low ambient temperatures, volume increases, and is more advantageous to suction of the activated carbon to impurity It is attached.
The cooling medium of deep freezer can be brine, freon or liquid nitrogen.The temperature model of the fixed gas exported from deep freezer Enclose is -50~-60 DEG C.
S210. the chlorosilane rich solution of two-stage hydrogen chloride absorption tower tower reactor output is carried out at parsing in hydrogen chloride Analytic Tower Reason to parse hydrogen chloride therein, and exports chlorosilane lean solution from tower reactor, light component is exported from tower top, then will be described light Group dispensing is recycled to downstream rectification working process using the chlorosilane lean solution as absorbing liquid.
In this step, the light component exported from hydrogen chloride Analytic Tower includes mainly hydrogen chloride gas, is also possible that certainly Micro impurity, such as micro dichlorosilane can remove therein miscellaneous after rectification working process carries out purification processes to it Matter obtains the higher hydrogen chloride gas of purity.The temperature range of the chlorosilane lean solution exported from hydrogen chloride Analytic Tower tower reactor is 120 ~130 DEG C.
S211. make the chlorosilane lean solution that hydrogen chloride Analytic Tower tower reactor exports after the cooling treatment of the second water cooler, it is defeated Enter to liquid-liquid heat exchanger.
In this step, the temperature range of the chlorosilane lean solution after the second water cooler cooling treatment is 40~50 DEG C.Second The cooling medium of water cooler is recirculated water.
S212. the chlorosilane rich solution and the second lime set of the output of two-stage hydrogen chloride absorption tower tower reactor are utilized in liquid-liquid heat exchanger The cold of the mixed liquor for the liquid-phase chlorosilane that storage tank is isolated is cooled down to what hydrogen chloride Analytic Tower tower reactor exported through the second water cooler The chlorosilane lean solution of processing carries out cooling treatment, and the mixed liquor for being then utilized cold is sent into hydrogen chloride Analytic Tower.
In this step, the chlorosilane rich solution and the liquid isolated of the second lime set storage tank of the output of two-stage hydrogen chloride absorption tower tower reactor The temperature range of the mixed liquor of phase chlorosilane is -30~-35 DEG C；The temperature model for the mixed liquor that cold has been utilized by liquid-liquid heat exchanger Enclose is 40~50 DEG C；Temperature range into the chlorosilane lean solution of liquid-liquid heat exchanger is 40~50 DEG C；It is cooled down through liquid-liquid heat exchanger The temperature range of chlorosilane lean solution afterwards is -20~-25 DEG C.
In addition, in order to preferably meet the operating pressure of two-stage hydrogen chloride absorption tower, more preferably, make hydrogen chloride Analytic Tower tower Kettle output through the chlorosilane lean solution of the second water cooler cooling treatment after circulating pump pressurizes reinfusate liquid heat exchanger.Its In, the pressure limit of the liquid of circulating pump output is 2.5~2.8MPaG.
In practical applications, if the absorbent (chlorosilane lean solution) for being input to two-stage hydrogen chloride absorption tower has been more than best inhales Dosage is received, in order to avoid waste, the chlorosilane lean solution after the second water cooler cooling treatment is divided into two parts, a portion It is sent into liquid-liquid heat exchanger, another part is sent into downstream rectification working process, to carry out the separation of chlorosilane component.It is changed as liquid liquid is sent into The amount of hot device part chlorosilane lean solution can be adjusted according to equipment actual conditions.
It S213. will be by the conduct after the cooling of the second freon condenser of liquid-liquid heat exchanger chlorosilane lean solution after cooling Absorbent is sent into two-stage hydrogen chloride absorption tower top.
In this step, using the chlorosilane lean solution after deep cooling as the absorbent of two-stage hydrogen chloride absorption tower, and abovementioned steps In S207 using compressor pair the second lime set storage tank isolate and cold by gas-gas heat exchanger using gaseous mixture rise It is re-fed into two-stage hydrogen chloride absorption tower after pressure processing, so that two-stage hydrogen chloride absorption tower is handled under conditions of high pressure low temperature The gaseous mixture carries out absorption processing to hydrogen chloride therein and partial impurities, and the chlorosilane rich solution obtained after absorption is sent to chlorine Change hydrogen Analytic Tower so that chlorination Analytic Tower also carries out dissection process under conditions of high-temperature low-pressure to chlorosilane rich solution, after parsing An obtained chlorosilane lean solution part is recycled as absorbent by circulating pump, another part send to downstream rectification working process into Row processing.
Wherein, the temperature range through the second freon condenser chlorosilane lean solution after cooling is -40~-45 DEG C.Input Amount to the chlorosilane lean solution on every absorption tower top can be adjusted according to equipment actual conditions.
In the present embodiment, above-mentioned steps S204~S207, step S211 and step S213 are optional step.
Wherein, if without step S204~S207, step S201 can be with the reversed order of step S202, and after reversed order Gas-gas heat exchanger utilizes the cold from the first lime set storage tank (gaseous mixture isolated) to restoring tail gas in new step S201 Cooling treatment is carried out, and exports gas-liquid mixture, gas gas is changed using the first water cooler in new step S202 after reversed order The gas-liquid mixture of hot device output carries out cooling treatment, to be formed and export gas-liquid mixture；It is solidifying using first in step S203 The gas-liquid mixture of the first water cooler of liquid storage tank pair output carries out gas-liquid separation processing；Two-stage hydrogen chloride absorption tower in step S208 Using in tower top-down that the first lime set of chlorosilane lean solution pair storage tank is isolated and cold has been utilized by gas-gas heat exchanger Hydrogen chloride in gaseous mixture carries out absorption processing, and the chlorosilane rich solution of tower reactor output is not mixed with any other liquid and is fed to Hydrogen chloride Analytic Tower.
If the gas-liquid mixture for utilizing the second lime set storage tank to export brine condenser without step S205, in step S206 Carry out cooling treatment.
If without step S211, in step S212 liquid-liquid heat exchanger directly to hydrogen chloride Analytic Tower tower reactor output without The chlorosilane lean solution of any other processing carries out cooling treatment.
Appoint if also needing to be not added with by liquid-liquid heat exchanger chlorosilane lean solution after cooling without step S213, in step S212 What he handles and is just sent directly into two-stage hydrogen chloride absorption tower top.
It should be noted that the step of step S201 to S213 in the present embodiment sequence does not absolutely represent each step and exists Sequencing when execution.
The present embodiment the method can be referred to mutually with the correlated characteristic in 1 the method for embodiment.
Polycrystalline silicon reduction exhaust deep-purifying method described in the present embodiment uses a kind of new reduction tail-gas deep purification Technique mainly optimizes recycling hydrogen purification process, under the premise of ensureing that reduction tail gas is sufficiently separated, shortens optimization Low pressure condenser system and recycling hydrogen purify technological process.It uses, and " (reduction tail gas passes through the first water cooling for low-pressure area gas-liquid separation Deep cooling is no longer carried out after device, and the cold of low-pressure area (cold for the liquid-phase chlorosilane that the second lime set storage tank is isolated) is transferred to Higher-pressure region), higher-pressure region low-temperature deep absorbs, successively through acticarbon absorption and silica gel absorption after recycling hydrogen low temperature " Flow, has well solved that complicated current reduction tail gas process, reduction tail gas clean-up high energy consumption, recycling hydrogen quality is not high, returns Receive the problems such as hydrogen carbon impurity concn is high, the requirement of electron level is not achieved in product.
Embodiment 3：
The present embodiment provides a kind of polycrystalline silicon reduction exhaust advanced purification system, the reduction tail gas comes from upstream polysilicon Production process specifically includes the gaseous mixture of hydrogen, hydrogen chloride, chlorosilane and a small amount of impurity, wherein chlorosilane includes four chlorinations The gaseous mixture of silicon, trichlorosilane and dichlorosilane, the impurity include phosphorus, boron, iron etc., and impurity containing in restoring tail gas Amount is 2ppm~5ppm.
As shown in Figures 3 and 4, the purification system includes multistage cooling equipment, the first lime set storage tank 4, the suction of two-stage hydrogen chloride Receive tower 11 and 12, active carbon adsorption column 19, silica gel adsorption column 20, hydrogen chloride Analytic Tower 14 and liquid-liquid heat exchanger 13.
The multistage cooling equipment is used to receive the reduction tail gas 1 from upstream production of polysilicon process, and to institute It states reduction tail gas and carries out multistage cooling treatment successively, to be formed and export gas-liquid mixture.Wherein multistage cooling equipment output Gas-liquid mixture includes the gaseous mixture of hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of impurity and condensed Liquid-phase chlorosilane.
In the present embodiment, the multistage cooling equipment includes that at least two-stage cools down equipment.
The first lime set storage tank 4 is used to carry out gas-liquid separation processing to the gas-liquid mixture of multistage cooling equipment output, With by the gas-liquid mixture hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of impurity gaseous mixture with it is cold Solidifying liquid-phase chlorosilane separation, then send the condensed liquid-phase chlorosilane to downstream rectification working process, with to liquid phase chlorine silicon Trichlorosilane, silicon tetrachloride and dichlorosilane in alkane carry out separating-purifying.The multistage cooling equipment utilization comes from first The cold of the gaseous mixture of lime set storage tank 4 carries out cooling treatment to the reduction tail gas.
The two-stage hydrogen chloride absorption tower 11 and 12 is used for using top-down chlorosilane lean solution in tower to coming from first Lime set storage tank 4 and cold absorption processing is carried out by the hydrogen chloride in the gaseous mixture of multistage cooling equipment utilization, and from tower reactor Chlorosilane rich solution is exported, fixed gas is exported from tower top.
The active carbon adsorption column 19 and the silica gel adsorption column 20 are orderly used to carries out adsorption treatment to the fixed gas And pure hydrogen is formed, the pure hydrogen is sent to upstream production of polysilicon process.
In the present embodiment, the fixed gas exported from two-stage hydrogen chloride absorption tower 11 and 12 tower tops is the hydrogen containing a small amount of impurity Gas can effectively remove impurity therein after the adsorption treatment of active carbon adsorption column 19, but it is miscellaneous also to introduce carbon simultaneously Matter after the adsorption treatment using silica gel adsorption column 20, can effectively remove carbon impurity, to obtain pure hydrogen.Then Obtained pure hydrogen is sent into the production of polysilicon process of upstream, to prepare polysilicon.
In addition, the connection type of the two-stage hydrogen chloride absorption tower 11 and 12 is specially：To be input to two-stage hydrogen chloride When the gaseous mixture on absorption tower 11 and 12 meets preset condition, the two-stage hydrogen chloride absorption tower 11 and 12 is connected in parallel；Wait for it is defeated Enter when not meeting preset condition to the gaseous mixture of two-stage hydrogen chloride absorption tower 11 and 12, the two-stage hydrogen chloride absorption tower 11 and 12 It is connected in series with.Certainly, two-stage hydrogen chloride absorption tower 11 and 12 is connected in parallel and is connected in series with and can switch at any time, you can at any time will It is switched to the mode of being connected in series in parallel two-stage hydrogen chloride absorption tower, will can also be at any time and be connected in series with mode Two-stage hydrogen chloride absorption tower be switched to parallel, can specifically be realized by pipeline and the control of simple valve.
More preferably, the preset condition is：Into hydrogen chloride gas in the gaseous mixture of two-stage hydrogen chloride absorption tower 11 and 12 Content within 50ppm, the total content of phosphorus, boron and iron tramp is within 1ppm.
In practical applications, also connection type in parallel or series can be selected according to actual production demand, to improve reality Flexibility in the production of border and production of units efficiency, the continuous and stable operation of safeguards system high efficiency, high quality.For example, being When system is contaminated or there is fluctuation, may be selected to be connected in series in start-up, the quality of the recycling hydrogen of tower top output at this time Mode improves hydrogen quality to increase absorption tower height degree；The side of being connected in parallel may be selected when the hydrogen quality of tower top output is stablized Formula improves absorption tower treating capacity to increase absorption tower tower diameter.The quality of hydrogen is usually to stablize under certain normal operation , parallel running mode is preferentially selected at this time, to improve production capacity.
Wherein, as shown in figure 3, the two-stage hydrogen chloride absorption tower 11 and 12, which is connected in parallel, refers to absorption tower 11 and suction Gas inlet pipe line, overhead gas export pipeline and the tower reactor liquid export line for receiving tower 12 are connected in parallel respectively, so that cold Gaseous mixture of the amount by multistage cooling equipment utilization is input to two hydrogen chloride absorption towers 11 and 12, and this two hydrogen chloride simultaneously Pass through the suction of active carbon adsorption column 19 and silica gel adsorption column 20 after the fixed gas mixing of absorption tower 11 and the output of 12 tower tops successively again Attached processing is re-fed into liquid-liquid heat exchanger 13 after the chlorosilane rich solution mixing of this two hydrogen chloride absorption tower tower reactor outputs；
As shown in figure 4, the two-stage hydrogen chloride absorption tower 11 and 12 is connected in series with and refers to the second hydrogen chloride absorption tower 12 Gas inlet pipe line and multistage cooling equipment (in gas-gas heat exchanger 3) be connected, the tower overhead gas of the second hydrogen chloride absorption tower 12 Body export pipeline is connected with the gas inlet pipe line of the first hydrogen chloride absorption tower 11, the overhead gas of the first hydrogen chloride absorption tower 11 Export pipeline (passing through deep freezer 18) is connected with active carbon adsorption column 19, and the tower reactor liquid of two-stage hydrogen chloride absorption tower 11 and 12 is defeated Go out pipeline parallel connection, so that gaseous mixture of the cold by multistage cooling equipment utilization is merely entered to the second hydrogen chloride absorption tower 12, The fixed gas exported from 12 tower top of the second hydrogen chloride absorption tower is input to the first hydrogen chloride absorption tower 11 again, is inhaled from the first hydrogen chloride The fixed gas for receiving the output of 11 tower top of tower passes through the adsorption treatment of active carbon adsorption column 19 and silica gel adsorption column 20, and the first chlorine successively It is re-fed into liquid-liquid heat exchanger after changing the chlorosilane rich solution mixing of the tower reactor output of hydrogen absorption tower 11 and the second hydrogen chloride absorption tower 12 13。
The chlorosilane rich solution that the hydrogen chloride Analytic Tower 14 is used to export two-stage hydrogen chloride absorption tower 11 and 12 tower reactors into Row dissection process, and chlorosilane lean solution is exported from tower reactor, light component is exported from tower top, then send the light component to downstream fine Evaporate process.
In the present embodiment, the light component exported from hydrogen chloride Analytic Tower 14 includes mainly hydrogen chloride gas, is also possible to certainly Including micro impurity, such as micro dichlorosilane, after rectification working process carries out purification processes to it, can remove therein Impurity obtains the higher hydrogen chloride gas of purity.
The chlorosilane rich solution that the liquid-liquid heat exchanger 13 is used to export using two-stage hydrogen chloride absorption tower 11 and 12 tower reactors Cold carries out cooling treatment to the chlorosilane lean solution that 14 tower reactor of hydrogen chloride Analytic Tower exports, and then send chlorosilane lean solution after cooling Enter two-stage hydrogen chloride absorption tower 11 and 12 tops, and by the cold from two-stage hydrogen chloride absorption tower 11 and 12 tower reactors by liquid The chlorosilane rich solution that liquid heat exchanger 13 utilizes is sent into hydrogen chloride Analytic Tower 14.
Polycrystalline silicon reduction exhaust advanced purification system described in the present embodiment is effectively utilized what the first lime set storage tank was isolated The cold of the chlorosilane rich solution of cold and two-stage hydrogen chloride absorption tower the tower reactor output of gaseous mixture, both has preferable separating effect (isolating liquid-phase chlorosilane, hydrogen and hydrogen chloride successively), and system cold is fully utilized, therefore public work cold consumes It is few, to reduce production cost；Using silica gel adsorption column by active carbon adsorption column treated the hydrogen containing carbon impurity again Secondary carry out adsorption treatment, has effectively removed carbon impurity therein so that recycling hydrogen is meeting accordingly wanting for electronic-grade polycrystalline silicon While asking (hydrogen chloride content ＜ 50ppm, carbon content ＜ 3ppm), the impurity content entrained by recycling hydrogen is effectively reduced, And reduce active carbon adsorption column delay time, active carbon adsorption column usage time is increased, recycling hydrogen purification is reduced Time.
Embodiment 4：
The present embodiment provides a kind of polycrystalline silicon reduction exhaust advanced purification systems.As it can be seen in figures 5 and 6, the purification system Including the first water cooler 2, gas-gas heat exchanger 3, the first lime set storage tank 4, the first delivery pump 5, brine condenser 6, the first freon Condenser 7, the second lime set storage tank 8, the second delivery pump 9, compressor 10, two-stage hydrogen chloride absorption tower 11 and 12, liquid-liquid heat exchanger 13, hydrogen chloride Analytic Tower 14, the second water cooler 15, circulating pump 16, the second freon condenser 17, deep freezer 18, activated carbon are inhaled Attached column 19 and silica gel adsorption column 20.It is connected by pipeline between above equipment, and pipeline and the junction of each equipment use method Orchid connection.
Moreover, the 2-9 in above equipment is all located at low-pressure area, pressure limit is 0.3~0.5MPa, preferably 0.45MPa. 10-20 in above equipment is all located at higher-pressure region, the pressure limit that wherein two-stage hydrogen chloride absorption tower 11 and 12 uses for 1.4~ 1.7MPa, preferably 1.6MPa；The pressure limit that hydrogen chloride Analytic Tower 14 uses is 0.7~0.9MPa, preferably 0.8MPa；It is living Property charcoal adsorption column 19 operating temperature range be -20~-50 DEG C, preferably -35 DEG C.
First water cooler 2 is used to receive the reduction tail gas from upstream production of polysilicon process by pipeline a, and right The reduction tail gas carries out cooling treatment, to be formed and export gas-liquid mixture to gas-gas heat exchanger 3 by line b.
It should be noted that in the present invention " gas-liquid mixture " of nearly all appearance all include hydrogen, hydrogen chloride, not by The gas phase chlorosilane of condensation and the gaseous mixture of a small amount of impurity and condensed liquid-phase chlorosilane, only different gas-liquid mixtures The accounting of middle each component is different.Wherein, the cooling medium of the first water cooler 2 is recirculated water；The gas-liquid of first water cooler 2 output is mixed 95% is gas phase in conjunction object.
In this step, the temperature range of the reduction tail gas 1 in pipeline a is 180~200 DEG C, under the temperature range Restoring tail gas is obtained after carrying out preliminary cooling treatment to the reduction tail gas that reduction furnace exports, and otherwise, restores heater outlet temperature It is excessively high, it is unfavorable for later stage recycling.
Tail gas 1 is restored after the cooling treatment of the first water cooler 2, temperature is greatly reduced, specially 40~50 DEG C (in line b) is convenient for the recycling of follow-up cold.
In addition, in order to ensure that the temperature of the gas-liquid mixture of the first water cooler 2 output meets above-mentioned temperature range requirements, compared with Excellently, measure and show the temperature of gas-liquid mixture in the export pipeline b of the first water cooler 2 in real time using temperature display meter, When the temperature that it is measured exceeds above-mentioned temperature range, the cold for being input to the first water cooler 2 can be increased in it The temperature of gas-liquid mixture is adjusted, to meet the requirement of above-mentioned temperature range.
Gas-gas heat exchanger 3 is used to utilize the first water cooling of cold pair from the second lime set storage tank 8 (gaseous mixture isolated) The gas-liquid mixture (i.e. 2 reduction tail gas after cooling of the first water cooler) that device 2 exports carries out cooling treatment, and defeated by line c Go out gas-liquid mixture to the first lime set storage tank 4.
Wherein, 70% is gas phase in the gas-liquid mixture that gas-gas heat exchanger 3 exports；Gas-gas heat exchanger 3 is exported by line c Gas-liquid mixture temperature range be -10~-15 DEG C.Moreover, pipeline a and c are connected to the shell side of gas-gas heat exchanger 3, pipeline i The tube side of gas-gas heat exchanger 3 is connected to j.
Restore tail gas 1 successively by the first water cooler 2, gas-gas heat exchanger 3 cooling treatment after, the gas-liquid mixture of formation The first lime set storage tank 4 is flowed by line c in a manner of gravity flow.
Gas-liquid mixture (the i.e. gas-gas heat exchanger 3 that first lime set storage tank 4 is used to export gas-gas heat exchanger 3 by line c Reduction tail gas after cooling) carry out gas-liquid separation processing, by the gas-liquid mixture hydrogen, hydrogen chloride, be not condensed The gaseous mixture of gas phase chlorosilane and a small amount of impurity is detached with condensed liquid-phase chlorosilane, and the gaseous mixture is then passed through pipeline F is exported to brine condenser 6；The condensed liquid-phase chlorosilane is sent by pipeline d to downstream rectification working process, with to liquid phase Trichlorosilane, silicon tetrachloride and dichlorosilane in chlorosilane carry out separating-purifying.
To meet the operating pressure (0.7MPaG or so) of downstream rectification working process, in the present embodiment, with the first lime set storage tank It is additionally provided with the first delivery pump 5 on the pipeline of 4 tank bottom connection, the liquid pressure range of output is 1.0~1.5MPaG, through the Liquid-phase chlorosilane after the pressurization of one delivery pump 5 is sent by pipeline e to downstream rectification working process again.Temperature of charge in pipeline d, e and f Range is also -10~-15 DEG C.
Tail gas 1 is restored after level-one water cooler 2 and gas-gas heat exchanger 3, a portion chlorosilane is condensed, also Dissolved hydrogen therein is effectively reduced, then after carrying out gas-liquid separation by the first lime set storage tank 4, by condensed liquid phase chlorine silicon Alkane is separated, and subsequent subzero treatment is no longer carried out, and is fed directly to downstream rectification working process and is carried out separating treatment, and not cold Solidifying gaseous mixture (i.e. the gaseous mixture of hydrogen, hydrogen chloride, the gas phase chlorosilane and a small amount of impurity that are not condensed) is as by preliminary Condensed gas is sent into brine condenser 6.
Brine condenser 6 is used to carry out cooling treatment to the gaseous mixture that the first lime set storage tank 4 is isolated, to be formed and be passed through Pipeline g exports gas-liquid mixture to the first freon condenser 7.
Wherein, the cooling medium of brine condenser 6 is chilled brine.
In the present embodiment, 95% or so is gas phase in the gas-liquid mixture that brine condenser 6 exports, thus by the first lime set Most of chlorosilane condensate in the gaseous mixture that storage tank 4 is isolated gets off.And.The gas-liquid mixture that brine condenser 6 exports Temperature range be -20~-23 DEG C (in pipeline g).
First freon condenser 7 is used to carry out cooling treatment to the gas-liquid mixture that brine condenser 6 exports, to be formed And gas-liquid mixture is exported to the second lime set storage tank 8 by pipeline h.
In the present embodiment, other gas for occurring in the gas-liquid mixture and the present embodiment of the output of the first freon condenser 7 The ingredient of liquid mixture is slightly different comprising hydrogen, the gaseous mixture of hydrogen chloride and a small amount of impurity and condensed liquid phase chlorine Silane, wherein be also 95% or so being gas phase, and gas-liquid mixture degree ranging from -35~-40 DEG C (in pipeline h).
(can be described as chlorosilane pre-separation) is detached since a chlorosilane being completed in the first lime set storage tank 4, and will be divided It separates out the liquid-phase chlorosilane come and send the cold consumption for correspondingly reducing chilled brine in brine condenser 6 to downstream rectification working process, And first freon in freon condenser 7 cold consumption, used with existing general reduction tail gas dry process recovery system Technique compare, save about 20% cold.
Second lime set storage tank 8 is used to carry out cooling treatment to the gas-liquid mixture that the first freon condenser 7 exports, will The gaseous mixture of hydrogen, hydrogen chloride and a small amount of impurity in the gas-liquid mixture is detached with condensed liquid-phase chlorosilane, will be described Gaseous mixture is exported by pipeline i to gas-gas heat exchanger 3, and the condensed liquid-phase chlorosilane is sent by pipeline p1 to higher-pressure region. It is inhaled moreover, the second lime set storage tank 8 is isolated and cold is admitted to two-stage hydrogen chloride by the gaseous mixture that gas-gas heat exchanger 3 utilizes Receive tower 11 and 12.
Wherein, the temperature range of gaseous mixture that the second lime set storage tank 8 is isolated and that cold has been utilized by gas-gas heat exchanger 3 For 5~10 DEG C (in pipeline j).
Successively by brine condenser 6, the first freon condenser 7 cooling treatment after, the first lime set storage tank 4 is detached Chlorosilane almost all in the gaseous mixture (i.e. aforementioned by preliminary condensed gas) gone out condenses out, to efficiently separate Go out by the light component in preliminary condensed gas, that is, realize being completely separated for light component and chlorosilane, and it is not solidifying only The gaseous mixture of hydrogen, hydrogen chloride and a small amount of impurity, using the separating treatment of the second lime set storage tank 8, in time by not solidifying hydrogen, The mixed gas separation of hydrogen chloride and a small amount of impurity comes.
In the present embodiment, the liquid-phase chlorosilane that the first lime set storage tank 4 is isolated is fed into the rectification working process in downstream, and not as The liquid-phase chlorosilane that second lime set storage tank 8 is isolated out like that is sent into the hydrogen chloride Analytic Tower 14 of higher-pressure region, is to mitigate The load of hydrogen chloride Analytic Tower 14.
In order to preferably meet the operating pressure of two-stage hydrogen chloride absorption tower 11 and 12, more preferably, make the second lime set storage tank 8 Isolate and cold is re-fed into higher-pressure region by the gaseous mixture that gas-gas heat exchanger 3 utilizes after the boosting of compressor 10 processing Two-stage hydrogen chloride absorption tower 11 and 12.In the present embodiment, compressor 10 is by the pressure limit of the pipeline k gaseous mixtures exported 1.5-1.7MPaG, temperature range are 5~10 DEG C.
In addition, in order to preferably meet the operating pressure of hydrogen chloride Analytic Tower 14, more preferably, the second lime set storage tank 8 is made to divide The liquid-phase chlorosilane separated out is sent by pipeline p2 to higher-pressure region and two-stage hydrogen chloride again after the boosting of the second delivery pump 9 processing Absorption tower 11 and 12 tower reactors are mixed by the chlorosilane rich solution of pipeline o1 and o2 output respectively.Second delivery pump is defeated by pipeline p1 The pressure limit of the liquid gone out is 1.8~2.0MPaG.Temperature of charge range in pipeline i, p1 and p2 is also -35~-40 DEG C.
Two-stage hydrogen chloride absorption tower 11 and 12 is used to utilize top-down the second lime set of chlorosilane lean solution pair storage tank 8 in tower Isolate and cold by gas-gas heat exchanger 3 using gaseous mixture eluted, to absorb hydrogen chloride therein, and from tower reactor Chlorosilane rich solution is exported, fixed gas (hydrogen containing a small amount of impurity), and two-stage hydrogen chloride absorption tower 11 and 12 are exported from tower top The liquid phase that tower reactor is exported by the chlorosilane rich solution and the second lime set storage tank 8 of pipeline o1 and o2 output by pipeline p1 and p2 respectively Chlorosilane mixed liquor is formed after chlorosilane mixing, is then exported to liquid-liquid heat exchanger 13, and two-stage hydrogen chloride absorption tower 11 and 12 The fixed gas of tower top output is exported by pipeline m and n to deep freezer 8.
In the present embodiment, into two-stage hydrogen chloride absorption tower 11 and 12 gaseous mixture with (from hydrogen chloride absorption tower top into Entering) top-down chlorosilane lean solution is in contact in tower so that and hydrogen chloride is dissolved in liquid-phase chlorosilane, to effectively remove Hydrogen chloride gas in the gaseous mixture improves the purity of hydrogen.
(parallel connection company is described in detail in embodiment 3 as the specific connection type of two-stage hydrogen chloride absorption tower 11 and 12 The mode of connecing refers to Fig. 5, and the mode of being connected in series with refers to Fig. 6), details are not described herein again.When two-stage hydrogen chloride absorption tower 11 and 12 uses When parallel, be input to the gaseous mixture on every absorption tower 11 or 12 amount can (such as tower top be defeated according to equipment actual conditions Quality, the produce load etc. of the recycling hydrogen gone out) it is adjusted, the suction of two-stage hydrogen chloride can be increased simultaneously when system throughput is big Receive the air inflow of tower 11 and 12.
Active carbon adsorption column 19 and silica gel adsorption column 20 are used to export not two-stage hydrogen chloride absorption tower 11 and 12 tower tops Solidifying gas carries out adsorption treatment to form pure hydrogen successively, and the pure hydrogen is admitted to upstream production of polysilicon work Sequence.Active carbon adsorption column 19 and silica gel adsorption column 20 are used in series, and the adsorbent of active carbon adsorption column 19 is activated carbon, silica gel The adsorbent of adsorption column 20 is silica gel.
In the present embodiment, the fixed gas that is exported from two-stage hydrogen chloride absorption tower 11 and 12 tower tops be containing a small amount of impurity (such as Phosphorus, boron, iron and micro chlorosilane etc.) hydrogen can be effectively removed after the adsorption treatment of active carbon adsorption column 19 Impurity such as phosphorus, boron, iron and micro chlorosilane therein, but can also introduce carbon impurity simultaneously, using with active carbon adsorption column The adsorption treatment of 19 concatenated silica gel adsorption columns 20, can effectively remove carbon impurity, keep the absorption that recycling hydrogen obtains depth net Change, to obtain recycling hydrogen that is pure, reaching qualified index, wherein content the ＜ 50ppm, carbon content ＜ of hydrogen chloride 3ppm.Then obtained pure recycling hydrogen is sent into the production of polysilicon process of upstream by pipeline s, to prepare polycrystalline Silicon.
In addition, in order to preferably meet the operating temperature of active carbon adsorption column 19 and silica gel adsorption column 20, adsorption column is improved Adsorption effect more preferably make at cooling of the fixed gas that two-stage hydrogen chloride absorption tower 11 and 12 tower tops export by deep freezer After reason, then pass sequentially through active carbon adsorption column 19 and silica gel adsorption column 20 so that active carbon adsorption column 19 is gone at low ambient temperatures Except impurity such as phosphorus, boron, the iron recycled in hydrogen, and these impurity are assembled at low ambient temperatures, and volume increases, and is more advantageous to Absorption of the activated carbon to impurity.
The cooling medium of deep freezer 18 can be brine, freon or liquid nitrogen.Deep freezer 18 is not coagulated by what pipeline q was exported The temperature range of gas is -50~-60 DEG C, and the temperature of charge in pipeline r and s is also -50~-60 DEG C.
Hydrogen chloride Analytic Tower 14 is used to solve the chlorosilane rich solution that two-stage hydrogen chloride absorption tower 11 and 12 tower reactors export Analysis is handled, and to parse hydrogen chloride therein, and exports chlorosilane lean solution from 14 tower reactor of hydrogen chloride Analytic Tower, light from tower top output Component.The light component is sent to downstream rectification working process by pipeline u, and the chlorosilane lean solution is exported by pipeline v, as suction Liquid is received to recycle.
In the present embodiment, the light component exported from hydrogen chloride Analytic Tower 14 includes mainly hydrogen chloride gas, is also possible to certainly Including micro impurity, such as micro dichlorosilane, after rectification working process carries out purification processes to it, can remove therein Impurity obtains the higher hydrogen chloride gas of purity.The temperature range of the chlorosilane lean solution exported from 14 tower reactor of hydrogen chloride Analytic Tower For 120~130 DEG C (in pipeline v).
Second water cooler 15 is used to carry out cooling treatment to the chlorosilane lean solution that 14 tower reactor of hydrogen chloride Analytic Tower exports, and leads to Pipeline w is crossed to export to liquid-liquid heat exchanger 13.
In the present embodiment, pass through the temperature model of the pipeline w chlorosilane lean solutions exported after 15 cooling treatment of the second water cooler Enclose is 40~50 DEG C.The cooling medium of second water cooler 15 is recirculated water.
The chlorosilane rich solution and second that liquid-liquid heat exchanger 13 is used to export using two-stage hydrogen chloride absorption tower 11 and 12 tower reactors The cold of the mixed liquor for the liquid-phase chlorosilane that lime set storage tank 8 is isolated to 14 tower reactor of hydrogen chloride Analytic Tower export through the second water cooling The chlorosilane lean solution of 15 cooling treatment of device carries out cooling treatment, is then sent into the mixed liquor that cold has been utilized by pipeline t Hydrogen chloride Analytic Tower.
In the present embodiment, the chlorosilane rich solution and the second lime set storage tank 8 of two-stage hydrogen chloride absorption tower 11 and the output of 12 tower reactors The temperature range of the mixed liquor for the liquid-phase chlorosilane isolated is -30~-35 DEG C (shell sides for entering liquid-liquid heat exchanger 13)；Cold The temperature range of the mixed liquor utilized by liquid-liquid heat exchanger 13 is 40~50 DEG C (by pipeline t from the shell of liquid-liquid heat exchanger 13 Journey exports)；Temperature range into the chlorosilane lean solution of liquid-liquid heat exchanger is 40~50 DEG C and (is entered by pipeline v, w, x and x1 The tube side of liquid-liquid heat exchanger 13)；Temperature range through liquid-liquid heat exchanger chlorosilane lean solution after cooling is -20~-25 DEG C and (passes through Pipeline y is exported from the tube side of liquid-liquid heat exchanger 13).
In addition, in order to preferably meet the operating pressure of two-stage hydrogen chloride absorption tower 11 and 12, more preferably, make chlorination hydrogenolysis Analysis 14 tower reactor of tower output passes through pipe again through the chlorosilane lean solution of 15 cooling treatment of the second water cooler after the pressurization of circulating pump 16 Line x inputs liquid-liquid heat exchanger 13.Wherein, the pressure limit that circulating pump 16 passes through the pipeline x liquid exported is 2.5~2.8MPaG.
In practical applications, if the absorbent (chlorosilane lean solution) for being input to two-stage hydrogen chloride absorption tower 11 and 12 has been more than Chlorosilane lean solution after 15 cooling treatment of the second water cooler is divided into two parts by optimal absorption dosage in order to avoid waste, A middle part is sent into liquid-liquid heat exchanger by pipeline x1, and another part is sent into downstream rectification working process by pipeline x2, to carry out chlorine The separation of silane components.The amount that liquid-liquid heat exchanger part chlorosilane lean solution is sent into as pipeline x1 can be according to equipment actual conditions It is adjusted.
Second freon condenser 17 by 13 chlorosilane lean solution after cooling of liquid-liquid heat exchanger for will further cool down It is used as absorbent to be sent into two-stage hydrogen chloride absorption tower 11 and 12 tops afterwards.
In the present embodiment, by 17 chlorine after cooling of the second water cooler 15, liquid-liquid heat exchanger 13 and the second freon condenser Absorbent of the silane lean solution as two-stage hydrogen chloride absorption tower 11 and 12, and second lime set storage tank 8 is detached using compressor 10 Go out and cold by gas-gas heat exchanger 3 using gaseous mixture carry out boosting processing after be re-fed into 11 He of two-stage hydrogen chloride absorption tower 12, so that two-stage hydrogen chloride absorption tower 11 and 12 handles the gaseous mixture under conditions of high pressure low temperature, to chlorine therein Change hydrogen and partial impurities carry out absorption processing, the chlorosilane rich solution obtained after absorption is sent to hydrogen chloride Analytic Tower 14 so that chlorination Analytic Tower 14 also carries out dissection process, the chlorosilane lean solution one obtained after parsing under conditions of high-temperature low-pressure to chlorosilane rich solution Part is recycled as absorbent by circulating pump, and another part send to downstream rectification working process and handled.
Wherein, the temperature range through 17 chlorosilane lean solution after cooling of the second freon condenser is -40~-45 DEG C of (pipes Line z, z1 and z2).Being input to the amount of the chlorosilane lean solution on every absorption tower 11 or 12 tops can carry out according to equipment actual conditions Adjustment.
In the present embodiment, brine condenser 6, the first freon condenser 7,8 second water cooler 15 of the second lime set storage tank, Two freon condensers 17 and deep freezer 18 are optional equipment.
As it can be seen that the main device of purification system described in the present embodiment includes condenser group, heat exchanger group, tank battery, compression Machine, rectifying column, adsorption column group and pump, the above equipment are attached according to the respectively different pipelines that acts through, gas condensation And absorption is carried out using series system.
Wherein, the condenser group includes the first water cooler 2, the second water cooler 15, brine condenser 6, the first freon Condenser 7, the second freon condenser 17 and deep freezer 18；The heat exchanger group includes gas-gas heat exchanger 3 and liquid-liquid heat exchanger 13；The tank battery includes the first lime set storage tank 4 and the second lime set storage tank 8；The compressor is piston compressor 10；It is described Rectifying column includes two-stage hydrogen chloride absorption tower 11 and 12 and hydrogen chloride Analytic Tower 14, and two-stage hydrogen chloride absorption tower 11 and 12 can To be connected in parallel, can also be connected in series with；The adsorption column group includes active carbon adsorption column 19 and silica gel adsorption column 20；The machine Pump includes the first delivery pump 5, the second delivery pump 9 and circulating pump 16.
The operation principle of purification system described in the present embodiment is described in detail below by specific example.
Definition：Inlet amount is 50m3/h；Restore exhaust gas composition：Trichlorosilane, silicon tetrachloride, dichlorosilane, hydrogen, chlorine Change the impurity such as hydrogen and a small amount of phosphorus, boron, iron.
So that the reduction tail gas 1 of high temperature is passed through the condensation of the first water cooler 2 and gas-gas heat exchanger 3, heat exchange successively, obtains initial set Liquid chlorosilane liquid produced and gas Jing Guo initial gross separation, it is solidifying that obtained pre-hardening liquid chlorosilane liquid produced by gravity flow mode flow to first Liquid storage tank 4, and given to the processing of downstream rectification working process by the first delivery pump 5.
The gas obtained after initial gross separation is subjected to depth by brine condenser 6 and the first freon condenser 7 Condensation, fixed gas and chlorosilane are thoroughly detached, and are sent into the second lime set storage tank 8, are carried out in the second lime set storage tank 8 Gas-liquid separation, obtained gas, which enters after the heat exchange of gas-gas heat exchanger 3 in compressor 10, carries out compression boosting, and obtained chlorine Silane liquid send to higher-pressure region by the second delivery pump 9 and is recycled as absorbing liquid.
10 compressed gas of compressor is sent into two-stage hydrogen chloride absorption tower 11 and 12, and passes through hydrogen chloride Analytic Tower Chlorosilane lean solution is exported from tower reactor after 14 parsings, after pressurizeing by the condensation of the second water cooler 15 and circulating pump 16, then passes through liquid Liquid heat exchanger 13 exchanges heat, and the chlorosilane lean solution after heat exchange is inhaled after 17 subzero treatment of the second freon condenser as absorption tower Agent is received, is entered in two-stage hydrogen chloride absorption tower 11 and 12, is exchanged heat through gas-gas heat exchanger 3 to what the second lime set storage tank 8 was isolated Treated, and gas carries out elution absorption processing, and chlorosilane rich solution is obtained after absorption and contains only the hydrogen of a small amount of impurity (wherein Two-stage hydrogen chloride absorption tower 11 and 12 can be according to the quality and absorption tower load selection serial or parallel connection mode of recycling hydrogen).
The rich solution chlorosilane obtained after absorption is sent and carries out dissection process into hydrogen chloride Analytic Tower 14, by chlorination therein Hydrogenolysis is sent to downstream process by tower top after separating out and is used, and the chlorosilane lean solution formed after parsing makes as absorbent cycle With.
The recycling hydrogen of two-stage hydrogen chloride absorption column overhead output passes through depth device 18, cools down to recycling hydrogen, drops The impurity such as chlorosilane and phosphorus, boron, iron of the recycling hydrogen by the pettiness content in active carbon adsorption column removal hydrogen after temperature, so The carbon molecules in recycling hydrogen are removed by silica gel adsorption column afterwards, the carbon impurity in recycling hydrogen are reduced, by the above processing stream The higher recycling hydrogen of purity obtained after journey, which is sent to polycrystalline reduction process, to be recycled.
Each equipment optimized operation parameter see the table below in system.
Table 1
System described in the present embodiment can be referred to mutually with the correlated characteristic in system described in embodiment 3.
Polycrystalline silicon reduction exhaust advanced purification system described in the present embodiment uses a kind of new reduction tail-gas deep purification Technique mainly optimizes recycling hydrogen purification process, under the premise of ensureing that reduction tail gas is sufficiently separated, shortens optimization Low pressure condenser system and recycling hydrogen purify technological process.It uses, and " (reduction tail gas passes through the first water cooling for low-pressure area gas-liquid separation Deep cooling is no longer carried out after device, and the cold of low-pressure area (cold for the liquid-phase chlorosilane that the second lime set storage tank is isolated) is transferred to Higher-pressure region), higher-pressure region low-temperature deep absorbs, successively through acticarbon absorption and silica gel absorption after recycling hydrogen low temperature " Flow, has well solved that complicated current reduction tail gas process, reduction tail gas clean-up high energy consumption, recycling hydrogen quality is not high, returns Receive the problems such as hydrogen carbon impurity concn is high, the requirement of electron level is not achieved in product.In addition, purification system described in the present embodiment is related to Equipment it is less, equipment failure rate is low, under the premise of ensureing product quality, can realize that system is run steadily in the long term.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses Mode, however the present invention is not limited thereto.For those skilled in the art, in the essence for not departing from the present invention In the case of refreshing and essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection scope of the present invention.

Claims (12)

1. a kind of polycrystalline silicon reduction exhaust deep-purifying method, the reduction tail gas includes hydrogen, hydrogen chloride, chlorosilane and a small amount of The gaseous mixture of impurity, which is characterized in that include the following steps：
Make multistage cooling treatment of the reduction tail gas successively by multistage cooling equipment, to form and export gas-liquid mixture, It includes the gaseous mixture of hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of impurity and condensed liquid phase chlorine silicon Alkane；
Gas-liquid separation processing is carried out to the gas-liquid mixture of multistage cooling equipment output using the first lime set storage tank, by the gas-liquid The gaseous mixture of hydrogen, hydrogen chloride, the gas phase chlorosilane and a small amount of impurity that are not condensed in mixture and condensed liquid phase chlorine Silane detaches, and then send the condensed liquid-phase chlorosilane to downstream rectification working process, and is utilized in the cooling equipment of multistage The cold of gaseous mixture from the first lime set storage tank carries out cooling treatment to the reduction tail gas；
Using top-down chlorosilane lean solution in tower to from the first lime set storage tank and cold in two-stage hydrogen chloride absorption tower Amount carries out absorption processing by the hydrogen chloride in the gaseous mixture of multistage cooling equipment utilization, and exports chlorosilane rich solution from tower reactor, Fixed gas is exported from tower top, then the fixed gas is made to pass through the adsorption treatment of active carbon adsorption column and silica gel adsorption column successively with shape At pure hydrogen, then the pure hydrogen is sent to upstream production of polysilicon process；
Dissection process is carried out to the chlorosilane rich solution of two-stage hydrogen chloride absorption tower tower reactor output in hydrogen chloride Analytic Tower, and from tower Kettle exports chlorosilane lean solution, exports light component from tower top, then send the light component to downstream rectification working process；
Hydrogen chloride is parsed using the cold of the chlorosilane rich solution of two-stage hydrogen chloride absorption tower tower reactor output in liquid-liquid heat exchanger The chlorosilane lean solution of tower tower reactor output carries out cooling treatment, and chlorosilane lean solution after cooling is then sent into two-stage hydrogen chloride absorption tower Top, and the chlorosilane rich solution that the cold from two-stage hydrogen chloride absorption tower tower reactor has been utilized by liquid-liquid heat exchanger are sent into chlorine Change hydrogen Analytic Tower.
2. purification method according to claim 1, which is characterized in that described to make the reduction tail gas successively by multistage cold But the multistage cooling treatment of equipment, to be formed and the step of exporting gas-liquid mixture is specially：
Cooling treatment is carried out to the reduction tail gas using the first water cooler；
The first water cooler of cold pair for the gaseous mixture isolated using the first lime set storage tank in gas-gas heat exchanger is after cooling also Protocercal tail gas carries out cooling treatment again,
To make the reduction tail gas pass through the cooling treatment of the first water cooler, gas-gas heat exchanger successively to form gas-liquid mixed Object.
3. purification method according to claim 2, which is characterized in that the purification method further includes：
Cooling treatment is carried out using the gaseous mixture that brine condenser pair the first lime set storage tank is isolated, it is mixed to form and export gas-liquid Close object comprising hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of impurity gaseous mixture and condensed liquid Phase chlorosilane；
Gas-liquid separation processing is carried out to the gas-liquid mixture that brine condenser exports using the second lime set storage tank, which is mixed The gaseous mixture and condensed liquid phase chlorine silicon of hydrogen, hydrogen chloride, the gas phase chlorosilane not being condensed and a small amount of impurity in conjunction object Alkane detaches, and after the first water cooler of the cold pair cooling for the gaseous mixture isolated using the second lime set storage tank in gas-gas heat exchanger Reduction tail gas carry out cooling treatment, and liquid-phase chlorosilane that the second lime set storage tank is isolated and two-stage hydrogen chloride absorption tower Chlorosilane mixed liquor is formed after the chlorosilane rich solution mixing of tower reactor output；
It is being isolated using top-down the second lime set of chlorosilane lean solution pair storage tank in tower in two-stage hydrogen chloride absorption tower and Cold by gas-gas heat exchanger using gaseous mixture in hydrogen chloride carry out absorption processing, and export chlorosilane rich solution from tower reactor, Fixed gas is exported from tower top；
Dissection process is carried out to the chlorosilane mixed liquor in hydrogen chloride Analytic Tower, and chlorosilane lean solution is exported from tower reactor, from Tower top exports light component；
The chlorosilane exported to hydrogen chloride Analytic Tower tower reactor using the cold of the chlorosilane mixed liquor in liquid-liquid heat exchanger is poor Liquid carries out cooling treatment, chlorosilane lean solution after cooling is then sent into two-stage hydrogen chloride absorption tower top, and will come from two-stage The chlorosilane rich solution that the cold of hydrogen chloride absorption tower tower reactor has been utilized by liquid-liquid heat exchanger is sent into hydrogen chloride Analytic Tower.
4. purification method according to claim 3, which is characterized in that the purification method further includes：
Cooling treatment is carried out to the gas-liquid mixture that brine condenser exports using the first freon condenser, to be formed and be exported Gas-liquid mixture comprising hydrogen, the gaseous mixture of hydrogen chloride and a small amount of impurity and condensed liquid-phase chlorosilane；
Cooling treatment is carried out using the gas-liquid mixture of second the first freon condenser of lime set storage tank pair output, by the gas-liquid The gaseous mixture of hydrogen, hydrogen chloride and a small amount of impurity in mixture is detached with condensed liquid-phase chlorosilane, and in gas-gas heat exchange The first water cooler of the cold pair reduction tail gas after cooling for the gaseous mixture isolated using the second lime set storage tank in device is cooled down Processing, and liquid-phase chlorosilane and the chlorosilane of two-stage hydrogen chloride absorption tower tower reactor output that the second lime set storage tank is isolated are rich Chlorosilane mixed liquor is formed after liquid mixing.
5. according to the purification method described in any one of claim 1-4, which is characterized in that inhaled to be input to two-stage hydrogen chloride When the gaseous mixture of receipts tower meets preset condition, two-stage hydrogen chloride absorption tower is made to be connected in parallel；It is inhaled to be input to two-stage hydrogen chloride When the gaseous mixture of receipts tower does not meet preset condition, two-stage hydrogen chloride absorption tower is made to be connected in series with.
6. purification method according to claim 5, which is characterized in that the preset condition is：It is inhaled into two-stage hydrogen chloride The content of hydrogen chloride gas in the gaseous mixture of tower is received within 50ppm, the total content of phosphorus, boron and iron tramp is within 1ppm.
7. a kind of polycrystalline silicon reduction exhaust advanced purification system, the reduction tail gas includes hydrogen, hydrogen chloride, chlorosilane and a small amount of The gaseous mixture of impurity, which is characterized in that including：The cooling equipment of multistage, the first lime set storage tank, two-stage hydrogen chloride absorption tower, activity Charcoal adsorption column, silica gel adsorption column, hydrogen chloride Analytic Tower and liquid-liquid heat exchanger,
The multistage cooling equipment is used for the reduction tail gas successively by the multistage cooling treatment of multistage cooling equipment, with shape At and export gas-liquid mixture comprising hydrogen, hydrogen chloride, the gas phase chlorosilane and a small amount of impurity that are not condensed gaseous mixture, And condensed liquid-phase chlorosilane；
The first lime set storage tank is used to carry out gas-liquid separation processing to the gas-liquid mixture of multistage cooling equipment output, should The gaseous mixture of hydrogen, hydrogen chloride, the gas phase chlorosilane and a small amount of impurity that are not condensed in gas-liquid mixture and condensed liquid Phase chlorosilane detaches, and the condensed liquid-phase chlorosilane is sent to downstream rectification working process, and the multistage cooling equipment utilization comes Cooling treatment is carried out to the reduction tail gas from the cold of the gaseous mixture of the first lime set storage tank；
The two-stage hydrogen chloride absorption tower is used for using top-down chlorosilane lean solution in tower to from the first lime set storage tank And cold carries out absorption processing by the hydrogen chloride in the gaseous mixture of multistage cooling equipment utilization, and it is rich from tower reactor output chlorosilane Liquid exports fixed gas from tower top；
The active carbon adsorption column and the silica gel adsorption column, which are orderly used to, to carry out adsorption treatment to the fixed gas and is formed pure Net hydrogen, the pure hydrogen are sent to upstream production of polysilicon process；
The chlorosilane rich solution that the hydrogen chloride Analytic Tower is used to export the two-stage hydrogen chloride absorption tower tower reactor carries out at parsing Reason, and chlorosilane lean solution is exported from tower reactor, light component is exported from tower top, the light component is sent to downstream rectification working process；
The liquid-liquid heat exchanger is used for the cold using the chlorosilane rich solution of two-stage hydrogen chloride absorption tower tower reactor output to institute The chlorosilane lean solution for stating the output of hydrogen chloride Analytic Tower tower reactor carries out cooling treatment, then will be described in chlorosilane lean solution feeding after cooling Two-stage hydrogen chloride absorption tower top, and the cold from the two-stage hydrogen chloride absorption tower tower reactor has been exchanged heat by the liquid liquid The chlorosilane rich solution that device utilizes is sent into the hydrogen chloride Analytic Tower.
8. purification system according to claim 7, which is characterized in that the multistage cooling equipment include the first water cooler and Gas-gas heat exchanger,
First water cooler is used to carry out cooling treatment to the reduction tail gas；
The cold for the gaseous mixture that the gas-gas heat exchanger is used to isolate using the first lime set storage tank is to first water cooling Device reduction tail gas after cooling carries out cooling treatment again, to make the reduction tail gas pass through the first water cooler, gas gas successively The cooling treatment of heat exchanger is to form gas-liquid mixture.
9. purification system according to claim 8, which is characterized in that the purification system includes brine condenser and second Lime set storage tank,
The brine condenser is used to carry out cooling treatment to the gaseous mixture that the first lime set storage tank is isolated, to be formed and export gas Liquid mixture comprising hydrogen, hydrogen chloride, the gaseous mixture of the gas phase chlorosilane not being condensed and a small amount of impurity and condensed Liquid-phase chlorosilane；
The second lime set storage tank is used to carry out gas-liquid separation processing to the gas-liquid mixture that the brine condenser exports, will The gaseous mixture of hydrogen, hydrogen chloride, the gas phase chlorosilane and a small amount of impurity that are not condensed in the gas-liquid mixture with it is condensed Liquid-phase chlorosilane detaches, the first water cooler of cold pair for the gaseous mixture that the gas-gas heat exchanger is isolated using the second lime set storage tank Reduction tail gas progress cooling treatment after cooling, and the liquid-phase chlorosilane that the second lime set storage tank is isolated and the two-stage chlorine Chlorosilane mixed liquor is formed after changing the chlorosilane rich solution mixing of hydrogen absorption tower tower reactor output；
The two-stage hydrogen chloride absorption tower is used for using top-down chlorosilane lean solution in tower to the second lime set storage tank point Separate out and cold by the gas-gas heat exchanger using gaseous mixture in hydrogen chloride carry out absorption processing, and exported from tower reactor Chlorosilane rich solution exports fixed gas from tower top；
The hydrogen chloride Analytic Tower is used to carry out dissection process to the chlorosilane mixed liquor, and poor from tower reactor output chlorosilane Liquid exports light component from tower top；
What the liquid-liquid heat exchanger was used to export the hydrogen chloride Analytic Tower tower reactor using the cold of the chlorosilane mixed liquor Chlorosilane lean solution carries out cooling treatment, and chlorosilane lean solution after cooling is then sent into the two-stage hydrogen chloride absorption tower top, with And the chlorosilane rich solution for having been utilized the cold from the two-stage hydrogen chloride absorption tower tower reactor by the liquid-liquid heat exchanger is sent into The hydrogen chloride Analytic Tower.
10. purification system according to claim 9, which is characterized in that the purification system further includes that the first freon is cold Condenser,
First freon condenser is used to carry out cooling treatment to the gas-liquid mixture that the brine condenser exports, with shape At and export gas-liquid mixture comprising hydrogen, the gaseous mixture of hydrogen chloride and a small amount of impurity and condensed liquid phase chlorine silicon Alkane；
The second lime set storage tank is used to carry out cooling treatment to the gas-liquid mixture that first freon condenser exports, with The gaseous mixture of hydrogen, hydrogen chloride and a small amount of impurity in the gas-liquid mixture is detached with condensed liquid-phase chlorosilane, it is described The first water cooler of cold pair for the gaseous mixture that gas-gas heat exchanger is isolated using the second lime set storage tank is after cooling to go back protocercal tail Gas progress cooling treatment, and the liquid-phase chlorosilane that the second lime set storage tank is isolated and the two-stage hydrogen chloride absorption tower tower reactor Chlorosilane mixed liquor is formed after the chlorosilane rich solution mixing of output.
11. according to the purification system described in any one of claim 7-10, which is characterized in that the two-stage hydrogen chloride absorption tower Connection type be specially：When the gaseous mixture to be input to two-stage hydrogen chloride absorption tower meets preset condition, the two-stage chlorine Change hydrogen absorption tower to be connected in parallel；When the gaseous mixture to be input to two-stage hydrogen chloride absorption tower does not meet preset condition, described two Grade hydrogen chloride absorption tower is connected in series with.
12. purification system according to claim 11, which is characterized in that the preset condition is：Into two-stage hydrogen chloride The content of hydrogen chloride gas is within 50ppm in the gaseous mixture on absorption tower, and the total content of phosphorus, boron and iron tramp is within 1ppm.
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